EP3712194A1 - Procédé de production de polyamide avec addition régulée d'activateur, et polyamide ainsi produit - Google Patents

Procédé de production de polyamide avec addition régulée d'activateur, et polyamide ainsi produit Download PDF

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Publication number
EP3712194A1
EP3712194A1 EP18878041.5A EP18878041A EP3712194A1 EP 3712194 A1 EP3712194 A1 EP 3712194A1 EP 18878041 A EP18878041 A EP 18878041A EP 3712194 A1 EP3712194 A1 EP 3712194A1
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EP
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Prior art keywords
polyamide
activator
weight
parts
group
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EP18878041.5A
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German (de)
English (en)
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EP3712194A4 (fr
Inventor
Hye Yeon Lee
Do Kyoung Kim
Seung Hoe Do
Jin Seo Lee
Kyung Ho Kwon
Dae Hak Kim
Kyoung Won YIM
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Hanwha Chemical Corp
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Hanwha Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
    • C08G69/14—Lactams
    • C08G69/16—Preparatory processes
    • C08G69/18—Anionic polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
    • C08G69/14—Lactams
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof

Definitions

  • the present invention relates to a method for producing a polyamide with controlled activator addition, and a polyamide produced thereby, and more particularly, to a method for producing a polyamide with controlled activator addition, and a polyamide produced thereby, the method allowing a polymerization conversion rate and a polydispersity index (PDI) to be enhanced by controlling the addition of an activator so as to prevent a gelation phenomenon that occurs during anionic polymerization.
  • PDI polydispersity index
  • a polyamide resin is a linear polymer bonded by an amide (-NHCO-) bond.
  • the polyamide resin is strong, has excellent physical properties in terms of friction resistance, abrasion resistance, oil resistance, and solvent resistance, and is easily melt-molded. Therefore, the polyamide resin is widely used as clothing materials, fibers for industrial materials, engineering plastics, and the like.
  • Polyamides may be classified into aliphatic polyamides, aromatic polyamides, and aliphatic cyclic polyamides according to molecular structures.
  • the aliphatic polyamides may be collectively referred to as nylon, and the aromatic polyamides may be collectively referred to as aramid.
  • Polyamides are produced by various polymerization methods and may be classified into those produced by ring-opening polymerization of lactam, such as nylon 6, those produced by polycondensation of diamines and dibasic acids, such as nylon 6,6, nylon 6,10 and nylon 4,6, and those produced by polycondensation of aminocarboxylic acids, such as nylon 11 and nylon 12.
  • lactam such as nylon 6, those produced by polycondensation of diamines and dibasic acids, such as nylon 6,6, nylon 6,10 and nylon 4,6, and those produced by polycondensation of aminocarboxylic acids, such as nylon 11 and nylon 12.
  • hybrid polymerized nylons such as hybrid condensates of caprolactam and 6,10-nylon salts (hexamethylenediamine and sebacate)
  • various polyamides including functional groups such as side chains and hydroxyl groups, aromatic rings and, hetero rings in molecules have been studied.
  • Lactams for example, caprolactam may be anionically polymerized.
  • This method generally uses a catalyst and an initiator (also referred to as an activator) (activated anionic polymerization).
  • initiator also referred to as an activator
  • US Patent No. 4,754,000 (Bayer AG) discloses activated anionic polymerization of lactams, which produces polyamides using biuret-group-containing polyisocyanates derived from non-aromatic diisocyanates as an activator.
  • EP 1091991 discloses a composition including polyisocyanurates having more than 3.5 NCO functional groups on average as a component A and a method for producing a surface coating composition using the composition.
  • a rubber i.e., elastomer
  • the resulting PA is up to 1.12 GPa and is not rigid.
  • the activator has a high weight average molecular weight (Mw). In this case, a large amount of activator is required (20% or more).
  • a mixture of a bifunctional activator and a multifunctional activator is used. Therefore, the resulting polyamide is not a crosslinked material.
  • US Patent No. 4,067,861 (1978 ) discloses a technology for anionic polymerization of lactams through an extruder.
  • a metering pump is installed between an extruder body and an extruder die so as to obtain a constant output and uniform viscosity and physical properties.
  • a reaction rate is fast due to a small molecular size in a process of adding an activator, but gelation occurs when an excessive amount is added at one time.
  • the present invention aims to solve the above-described problems of the related art and the technical problems requested from the past.
  • An object of the present invention is to provide a method for producing a polyamide with controlled activator addition, and a polyamide produced thereby, the method allowing a polymerization conversion rate and a polydispersity index (PDI) to be enhanced by controlling the addition of an activator so as to prevent a gelation phenomenon that occurs during anionic polymerization.
  • a polymerization conversion rate and a polydispersity index (PDI) to be enhanced by controlling the addition of an activator so as to prevent a gelation phenomenon that occurs during anionic polymerization.
  • Another object of the present invention is to provide a method for producing a polyamide with controlled activator addition, and a polyamide produced thereby, wherein the method is an eco-friendly processing method that does not generate by-products and does not use a solvent as a catalyst, and enables polymerization to a uniform molecular weight with a high conversion rate in a short polymerization reaction time at a low temperature, compared with an existing polymerization method.
  • a method for producing a polyamide with controlled activator addition is a method for producing a polyamide with controlled activator addition through an anionic polymerization reaction, wherein lactam, and based on 100 parts by weight of the entire lactam, 0.01 parts by weight to 20 parts by weight of an alkali metal as an initiator, 0.3 parts by weight to 10 parts by weight of a molecular weight controller, and 0.002 parts by weight to 7.0 part by weight of an activator are included, and the activator is injected by adjusting an addition amount at an interval of at least twice.
  • an addition interval of the activator may be within 1 minutes to 10 minutes.
  • an amount of the activator added once may be within a range of 0.002 parts by weight to 7.0 parts by weight.
  • the activator may include at least one selected from the group consisting of carbon dioxide (CO 2 ), benzoyl chloride, N-acetyl caprolactam, N-acetyl laurolactam, octadecyl isocyanate (SIC), toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI), and any mixture thereof.
  • CO 2 carbon dioxide
  • benzoyl chloride N-acetyl caprolactam
  • N-acetyl laurolactam N-acetyl laurolactam
  • SIC octadecyl isocyanate
  • TDI toluene diisocyanate
  • HDI hexamethylene diisocyanate
  • the activator may be injected in a spraying method using a sparger.
  • the activator may be injected into a polymer.
  • the activator may be injected by being sprayed onto the upper portion of the polymer, that is, the surface thereof.
  • an addition rate of the activator may be within a range of 0.001 L/min to 10 L/min with respect to a volume (1 m 3 ) of a reactor.
  • the alkali metal may include at least one selected from the group consisting of metal hydride, metal hydroxide, and metal alkoxide.
  • the polymerization reaction may be performed within a range of 0.5 minutes to 120 minutes.
  • the polymerization reaction is not particularly limited and may be appropriately adjusted according to a weight of a compound added or a size and a type of the reactor.
  • the lactam in the polymerization reaction may have a conversion rate of 95% or more.
  • the polymerization reaction may be performed within a range of 180°C to 300°C.
  • the present invention provides a polyamide produced by the method described above.
  • the polyamide may have a polydispersity index (PDI) of 3.0 or less.
  • PDI polydispersity index
  • a weight average molecular weight (Mw) of the polyamide may be in a range of 20,000 to 100,000.
  • the polyamide may have a linear, branched, hyperbranched, or dendritic structure.
  • the present invention provides a parts material selected from the group consisting of a vehicle material, an electronic device material, an industrial pipe material, a construction engineering material, a 3D printer material, a textile material, a cladding material, a machine tool material, a medical material, an aviation material, a photovoltaic material, a battery material, a sports material, a household appliance material, a household material, and a cosmetic material, which each include the polyamide.
  • a parts material selected from the group consisting of a vehicle material, an electronic device material, an industrial pipe material, a construction engineering material, a 3D printer material, a textile material, a cladding material, a machine tool material, a medical material, an aviation material, a photovoltaic material, a battery material, a sports material, a household appliance material, a household material, and a cosmetic material, which each include the polyamide.
  • a product including the parts material may be vehicle air ducts, plastic/rubber compounds, adhesives, lights, polymer optical fibers, fuel filter caps, line systems, cables for electronic devices, reflectors, sheaths of cables, optical fibers, wire protection tubes, control units, pipe tubes, liners, pipe coatings, oilfield exploration hoses, 3D printers, multifilaments, spray hoses, valves, ducts, pulps, gears, medical catheters, flame retardants for aircraft, solar cell protection plates, cosmetic materials, high hardness films, ski boots, headsets, glasses frames, toothbrushes, water bottles, or outsoles, but the present invention is not limited thereto.
  • the present invention provides a method for producing a polyamide with controlled activator addition, and a polyamide produced thereby, the method allowing a polymerization conversion rate and a polydispersity index (PDI) to be enhanced by controlling the addition of an activator so as to prevent a gelation phenomenon that occurs during anionic polymerization.
  • a polymerization conversion rate and a polydispersity index (PDI) to be enhanced by controlling the addition of an activator so as to prevent a gelation phenomenon that occurs during anionic polymerization.
  • the present invention is an eco-friendly processing method that does not generate by-products and does not use a solvent as a catalyst and has an effect that enables polymerization to a uniform molecular weight with a high conversion rate in a short polymerization reaction time at a low temperature, compared with an existing polymerization method.
  • the present invention also has an effect that a polymerization time is short and bulk polymerization is enabled, thereby greatly improving productivity through continuous processing, greatly increasing the efficiency of a manufacturing process, and greatly reducing manufacturing costs.
  • FIGS. 1 to 3 are configuration diagrams showing activator addition of a method for producing a polyamide with controlled activator addition according to the present invention.
  • substitution means that one or more hydrogen atoms in the functional groups of the present invention are substituted with one or more substituents selected from the group consisting of a halogen atom (-F, -Cl, -Br, or -I), a hydroxy group, a nitro group, a cyano group, an amino group, an amidino group, a hydrazine group, a hydrazone group, a carboxyl group, an ester group, a ketone group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alicyclic organic group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted heteroaryl group, and a
  • substituted means that a hydrogen atom is substituted with a substituent such as a halogen atom, a C 1 -C 20 hydrocarbon group, a C 1 -C 20 alkoxy group, and a C 6 -C 20 aryloxy group.
  • hydrocarbon group refers to a linear, branched, or cyclic saturated or unsaturated hydrocarbon group, and the alkyl group.
  • alkenyl group, the alkynyl group, and the like may be linear, branched, or cyclic.
  • alkyl group refers to a C 1 -C 30 alkyl group and the term “aryl group” refers to a C 6 -C 30 aryl group.
  • heterocyclic group refers to a group in which one to three heteroatoms selected from the group consisting of O, S, N, P, Si, and any combination thereof are contained in one ring. Examples of the heterocyclic group may include pyridine, thiophene, and pyrazine, but the present invention is not limited thereto.
  • the present invention provides a method for producing a polyamide with controlled activator addition by an anionic polymerization reaction, wherein lactam, and based on 100 parts by weight of the entire lactam, 0.01 parts by weight to 20 parts by weight of an alkali metal as an initiator, 0.3 parts by weight to 10 parts by weight of a molecular weight controller, and 0.002 parts by weight to 7.0 part by weight of an activator are included, and the activator is added by adjusting the amount of addition at least twice at certain time intervals, thereby providing the solution to the above-described problems.
  • the activator may be added at least twice at intervals of 1 minute to 10 minutes.
  • the activator may be added at least twice at intervals of 3 minutes to 7 minutes.
  • FIGS. 1 to 3 schematically show a state in which carbon dioxide is added as the activator to a polymer for producing a polyamide 12 according to the present invention.
  • a gelation phenomenon is prevented by injecting the carbon dioxide as the activator into the surface of the polymer at least twice at intervals of 5 minutes in a one-line manner, thereby improving a polymerization conversion rate and a polydispersity index (PDI).
  • PDI polydispersity index
  • the carbon dioxide may be injected as the activator by spraying the carbon dioxide at least twice at intervals of 5 minutes in a sparger manner.
  • the carbon dioxide may be directly injected as the activator into the polymer at least twice at intervals of 5 minutes in a one-line manner.
  • the PDI when the number of times of addition of the activator is less than twice, the PDI may increase. Therefore, it is preferable to add the activator at least twice.
  • the addition rate of the activator may be within a range of 0.001 L/min to 10 L/min with respect to the volume (1 m 3 ) of the reactor.
  • the activator may be more efficiently sprayed onto the polymer to improve polymerization efficiency and fundamentally prevent the gelation phenomenon.
  • compositions included in the production of the polyamide by the anionic ring-opening polymerization according to the present invention will be described below.
  • the laurolactam according to the present invention may be preferably used as a monomer for producing the polyamide.
  • the laurolactam may include caprolactam, piperidone, pyrrolidone, enantolactam, and caprylactam.
  • the lactam may include propiolactam, 2-pyrrolidone, valerolactam, caprolactam, heptanolactam, octanolactam, nonanolactam, decanolactam, undecanolactam, and dodecanolactam.
  • the alkali metal catalyst according to the present invention is an initiator for producing the polyamide and may include at least one selected from the group consisting of metal hydride, metal hydroxide, and metal alkoxide as a compound that allows the formation of the lactam anion.
  • the metal hydride may include sodium hydride and potassium hydride
  • the metal hydroxide may include sodium hydroxide and potassium hydroxide
  • the metal alkoxide may include potassium tetra-butoxide and aluminum isopropoxide, but the present invention is not limited thereto.
  • the metal alkoxide may include sodium caprolactamate or potassium caprolactamate, alkaline earth metal caprolactamate, for example, magnesium bromide caprolactamate, magnesium chloride caprolactamate, or magnesium biscaprolactamate, an alkali metal, for example, sodium or potassium, alkali metal base, for example, sodium base, for example sodium hydride, sodium, sodium hydroxide, sodium methanolate, sodium ethanolate, sodium propanolate, or sodium butanolate, or at least one selected from the group consisting of potassium base, for example potassium hydride, potassium, potassium hydroxide, potassium methanolate, potassium ethanolate, potassium propanolate, potassium butanolate, or any mixture thereof, preferably at least one selected from the group consisting of sodium caprolactate, potassium caprolactate, magnesium bromide caprolactate, magnesium chloride caprolactate, magnesium biscaprolactate, sodium hydride, sodium, sodium hydroxide, sodium ethanolate, sodium methanolate,
  • the metal catalyst may be used in the form of a solid or a solution, and the catalyst is preferably used in the form of a solid.
  • the catalyst is preferably added to a laurolactam melt in which the catalyst can be dissolved.
  • an amount of the alkali metal catalyst may be in a range of 0.01 parts by weight to 20 parts by weight based on 100 parts by weight of the entire lactam.
  • the amount of the alkali metal catalyst may be in a range of preferably 0.03 parts by weight to 10 parts by weight, and more preferably 0.05 parts by weight to 5 parts by weight.
  • the alkali metal catalyst when added in an amount of less than 0.01 parts by weight, unpolymerization may occur or a reaction rate may decrease.
  • the amount of the alkali metal catalyst exceeds 20 parts by weight, a low-molecular-weight polymer may be generated. Therefore, the above range is preferable.
  • the molecular weight controller according to the present invention may be preferably ethylene-bis-stearamide (EBS), but the present invention is not limited thereto.
  • the molecular weight controller may include at least one selected from the group consisting of an amine compound, a urea compound, and a di-urea compound.
  • an amount of the molecular weight controller may be in a range of 0.3 parts by weight to 10 parts by weight based on 100 parts by weight of the entire lactam.
  • the amount of the alkali metal catalyst may be in a range of preferably 0.4 parts by weight to 7 parts by weight, and more preferably 0.5 parts by weight to 3 parts by weight.
  • the molecular weight controller when added in an amount of less than 0.3 parts by weight, a gelation problem may occur. When the amount of the molecular weight controller exceeds 10 parts by weight, a low-molecular-weight polymer may be generated. Therefore, the above range is preferable.
  • the activator may preferably be carbon dioxide (CO 2 ), but the present invention is not limited thereto.
  • the activator may include at least one selected from the group consisting of benzoyl chloride, N-acetyl caprolactam, N-acetyl laurolactam, octadecyl isocyanate (SIC), toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI), and any mixture thereof.
  • an amount of the activator may be in a range of 0.002 parts by weight to 7.0 part by weight based on 100 parts by weight of the entire lactam.
  • the amount of the activator may be in a range of preferably 0.005 parts by weight to 5.0 parts by weight, and more preferably 0.01 parts by weight to 1.0 parts by weight.
  • a low-molecular-weight polymer when the activator is added in an amount of less than 0.002 parts by weight, a low-molecular-weight polymer may be produced by unpolymerization or a reaction rate may decrease.
  • the amount of the activator exceeds 7.0 part by weight, a gelation problem may occur or a low-molecular-weight polymer may be produced. Therefore, the above range is preferable.
  • Lactam (g) Alkali metal (g) Molecular weight controller (g) Content of CO 2 (ml) Addition method
  • Example 1 15 0.03 0.12 2(1+1) Twice
  • Example 2 15 0.03 0.12 20(10+10) Twice
  • Example 3 15 0.03 0.12 3(1+1+1) Three times
  • Example 4 15 0.03 0.12 2(1+1) Sparger surface addition (twice)
  • Example 5 15 0.03 0.12 2(1+1) one-line internal addition (twice)
  • Example 6 15 0.03 0.12 2(1+1) Addition after decompression inside reactor (0.9 bar) Comparative Example 1 15 0.03 0.12 20 One time Comparative Example 2 15 0.03 0.12 1000(500+5 00) Twice
  • a polyamide 12 sample was produced in the same manner as in Example 1, except that 10 ml of carbon dioxide was injected twice at intervals of 5 minutes.
  • a polyamide 12 sample was produced in the same manner as in Example 1, except that 1 ml of carbon dioxide was injected three times at intervals of 5 minutes.
  • a polyamide 12 sample was produced in the same manner as in Example 1, except that carbon dioxide was injected using sparger.
  • a polyamide 12 sample was produced in the same manner as in Example 1, except that carbon dioxide was injected into a solution by using one-line.
  • a polyamide 12 sample was produced in the same manner as in Example 1, except that an internal pressure of a reactor was lowered to 0.9 bar and carbon dioxide was injected into a solution by using one-line. The reaction was terminated after 35 minutes.
  • a polyamide 12 sample having a content shown in Table 2 was produced in the same manner as in Example 7, except that carbon dioxide was injected at the upper end of the solution at a rate of 800 ml/min for 45 seconds. After 13 minutes, the reaction was terminated.
  • Lactam (kg) Alkali metal (g) Molecular weight controller (g) Content of CO 2 (ml) CO 2 Injection rate
  • Example 7 3. 5 7.1 26 600 300 ml/min
  • a polyamide 12 sample was produced in the same manner as in Example 1, except that N-acetylcaprolactam (NAC) was injected instead of carbon dioxide and it was adjusted to include conditions shown in Table 3.
  • NAC N-acetylcaprolactam
  • Lactam g
  • Alkali metal g
  • Molecular Weight controller g
  • Content of NAC ml
  • Polymerization temperature °C
  • Example 9 20 0.12 0.24 0.80(0.4+0.4) 230
  • Example 10 20 0.12 0.14 0.80(0.4+0.4) 180
  • a polyamide 12 sample was produced in the same manner as in Example 1, except that 20 ml of carbon dioxide was injected at one time.
  • a polyamide 12 sample was produced in the same manner as in Example 1, except that 500 ml of carbon dioxide was injected twice at intervals of 5 minutes.
  • Comparative Example 1 in which 20 ml of carbon dioxide was injected as an activator at one time showed a high molecular weight and a wide molecular weight distribution outside a target range, compared with Example 1, and Comparative Example 2 in which 500 ml of carbon dioxide was injected twice at intervals of 5 minutes showed a very high molecular weight and a wide molecular weight distribution outside a target range, compared with Example 1.
  • Table 5 Molecular weight (g/mol) Polydispersity index (PDI) Polymerization time (min) Example 7 61,500 2.3 35
  • Example 8 which had a relatively fast carbon dioxide injection rate compared with Example 7, had a short polymerization time and a large molecular weight.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyamides (AREA)
EP18878041.5A 2017-11-14 2018-10-29 Procédé de production de polyamide avec addition régulée d'activateur, et polyamide ainsi produit Pending EP3712194A4 (fr)

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KR1020170151495A KR102262539B1 (ko) 2017-11-14 2017-11-14 활성화제 투입 방식 조절을 통한 폴리아마이드 제조방법 및 이에 의해 제조된 폴리아마이드
PCT/KR2018/012938 WO2019098569A1 (fr) 2017-11-14 2018-10-29 Procédé de production de polyamide avec addition régulée d'activateur, et polyamide ainsi produit

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EP3712194A1 true EP3712194A1 (fr) 2020-09-23
EP3712194A4 EP3712194A4 (fr) 2021-08-18

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EP (1) EP3712194A4 (fr)
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WO (1) WO2019098569A1 (fr)

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KR102560093B1 (ko) * 2019-12-06 2023-07-27 한화솔루션 주식회사 라우로락탐의 제조방법, 이의 합성장치, 이에 의해 제조된 라우로락탐 조성물, 이를 이용한 폴리라우로락탐의 제조방법
WO2021112495A1 (fr) * 2019-12-06 2021-06-10 한화솔루션 주식회사 Procédé de production d'un polyamide par polymérisation anionique et polyamide ainsi préparé

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JP6521951B2 (ja) 2013-06-12 2019-05-29 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ ポリアミドオリゴマーの連続式の製造方法及び部分結晶質又は非晶質の、熱塑性加工可能なポリアミドの製造方法
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KR20160037692A (ko) * 2014-09-29 2016-04-06 성균관대학교산학협력단 폴리아마이드의 제조방법
KR20160083649A (ko) * 2014-12-31 2016-07-12 코오롱플라스틱 주식회사 음이온 중합반응을 통한 폴리아미드 제조 방법

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KR102262539B1 (ko) 2021-06-08
JP2021502462A (ja) 2021-01-28
WO2019098569A1 (fr) 2019-05-23
US20200277438A1 (en) 2020-09-03
JP7431731B2 (ja) 2024-02-15
EP3712194A4 (fr) 2021-08-18
US11814480B2 (en) 2023-11-14
CN111433255A (zh) 2020-07-17

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